CN101381293B - Method for preparing high-purity beta-jonone - Google Patents
Method for preparing high-purity beta-jonone Download PDFInfo
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- CN101381293B CN101381293B CN2008101991970A CN200810199197A CN101381293B CN 101381293 B CN101381293 B CN 101381293B CN 2008101991970 A CN2008101991970 A CN 2008101991970A CN 200810199197 A CN200810199197 A CN 200810199197A CN 101381293 B CN101381293 B CN 101381293B
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- Prior art keywords
- lonone
- beta
- jononeionone
- alpha
- luolantong
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- 238000000034 method Methods 0.000 title claims abstract description 28
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 claims abstract description 32
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 14
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims description 9
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 3
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- SFEOKXHPFMOVRM-BQYQJAHWSA-N γ-ionone Chemical compound CC(=O)\C=C\C1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-BQYQJAHWSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000004587 chromatography analysis Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007363 ring formation reaction Methods 0.000 description 5
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- -1 citric acid aldehyde Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing high-purity beta-lonone. The method is to dissolve lonone in methanol and transform alpha-lonone or/and gamma-lonone into the beta-lonone under the catalysis of cuprous chloride and 300 to 325 nanometers of ultraviolet light. The method can obtain the high-purity beta-lonone (the content of the beta-lonone in the final product can reach 98 percent), has simple method and gentle condition without special instruments, thus the method is advantageous to industrial production.
Description
Technical field
The present invention relates to organic chemistry filed, be specifically related to prepare the method for alpha, beta-lonone.
Background technology
Highly purified alpha, beta-lonone (β-body 〉=95.0%) is the main raw material that medicine industry is produced vitamin A.The synthetic of alpha, beta-lonone is to generate pseudo ionone by citric acid aldehyde and condensation of acetone, formed by the pseudo ionone cyclisation under acidic conditions then.The generation of alpha, beta-lonone need be carried out at a lower temperature, but the cyclization very exothermic of aforesaid method, difficult control of temperature causes the jononeionone position of double bond to change, and resulting product is the mixture of α-Zi Luolantong, γ-jononeionone and alpha, beta-lonone normally.At this deficiency, German patent DE .3328440 has proposed a kind ofly at room temperature to contact the method for producing alpha, beta-lonone with sulfuric acid moment by pseudo ionone, but this method needs specific installation, condition control difficulty.Add dry ice when Chinese patent CN1508113 has also proposed to utilize cyclization and reduce the method that temperature of reaction improves alpha, beta-lonone purity, this method can make content 〉=96.0% of alpha, beta-lonone in the final product, and yield is 72～85.0%.Though can show effect preferably during the lab scale of this method laboratory, then have following shortcoming during scale operation: (1) adds the complicated operation of dry ice, make the production difficulty strengthen; (2) to take away the heat that produces rapidly in the cyclization process, otherwise produce a large amount of α-Zi Luolantongs and γ-jononeionone; When (3) a large amount of dry ice are added, if uniform contact reaction rapidly just can cause local superheating, produces isomer.
Summary of the invention
The technical problem to be solved in the present invention is further to improve alpha, beta-lonone purity when reducing the production operation difficulty.
The technical scheme that the present invention addresses the above problem is:
The method for preparing the high purity alpha, beta-lonone, this method is made up of following steps:
(1) cuprous chloride with jononeionone and jononeionone quality 2～3% is dissolved in the methyl alcohol;
(2) at room temperature be the UV-irradiation 0.5～1 hour of 300～325nm with wavelength;
(3) add the water ethyl acetate extraction, solvent evaporated, underpressure distillation gets product;
Described jononeionone is one or both in α-Zi Luolantong, the γ-jononeionone, or the mixture of one or both and alpha, beta-lonone in the α-Zi Luolantong, γ-jononeionone; The volume of used methyl alcohol is 1～1.5 times of jononeionone quality.
In the inventive method, described ultraviolet wavelength the best is 325nm.
In order to reach better changing effect, the inventive method step (1) cuprous chloride can add after jononeionone is dissolved in methyl alcohol again, jononeionone is dissolved in methyl alcohol that is:, adds the cuprous chloride of jononeionone quality 2～3% then.
The principle of the inventive method is: two bonding electron clouds resonate on α-Zi Luolantong, γ-jononeionone under the effect of cuprous chloride and UV-light, cause electronics to move to the most stable direction of gripping altogether, finally form alpha, beta-lonone.Following formula has reflected that α-Zi Luolantong is converted into the process of alpha, beta-lonone, and the conversion of γ-jononeionone in like manner.
The inventive method can be converted into alpha, beta-lonone with α-Zi Luolantong, γ-jononeionone, also pseudo ionone can be converted into alpha, beta-lonone by the inventive method with wherein α-Zi Luolantong, γ-jononeionone through the cyclization products therefrom, do not need painstakingly to control the temperature of cyclization, greatly reduce the difficulty of producing alpha, beta-lonone.Purity 〉=98.5% of the inventive method gained alpha, beta-lonone, yield are 95%, and method is simple, mild condition, do not need specific apparatus, helps suitability for industrialized production.
Embodiment
Example 1
The methanol solution that in reactor, adds 100 gram (0.5 rubs) α-Zi Luolantongs and 100 milliliters, the cuprous chloride that adds 3 grams then, at 30 ℃ down is the UV-irradiation 0.5 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 96 grams.
By gas chromatographic analysis, alpha, beta-lonone content is 98.6% in the product, and α-Zi Luolantong content is 0.8%.
Example 2
The methanol solution that in reactor, adds 100 gram (0.5 rubs) γ-jononeionones and 150 milliliters, the cuprous chloride that adds 2 grams then, at 25 ℃ down is the UV-irradiation 1 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 95.8 grams.
By gas chromatographic analysis, record that alpha, beta-lonone content is 98% in the product, γ-jononeionone content is 0.9%.
Example 3
The methanol solution that in reactor, adds 100 gram (0.5 rubs) α-Zi Luolantongs and 100 milliliters, the cuprous chloride that adds 3 grams then, at 30 ℃ down is the UV-irradiation 0.5 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 95.5 grams.
By gas chromatographic analysis, record that alpha, beta-lonone content is 97% in the product, α-Zi Luolantong content is 0.9%.
Example 4
The methanol solution that in reactor, adds 50 gram α-Zi Luolantongs and 50 gram γ-jononeionones and 100 milliliters, the cuprous chloride that adds 3 grams then, at 30 ℃ down is the UV-irradiation 0.5 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 96 grams.
By gas chromatographic analysis, record that alpha, beta-lonone content is 97% in the product, α-Zi Luolantong content is 0.8%, γ-jononeionone content 0.2%.
Example 5
The methanol solution that in reactor, adds 20 gram α-Zi Luolantongs and 80 gram alpha, beta-lonones and 100 milliliters, the cuprous chloride that adds 3 grams then, at 30 ℃ down is the UV-irradiation 0.5 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 96.5 grams.
By gas chromatographic analysis, record that alpha, beta-lonone content is 98.3% in the product, α-Zi Luolantong content is 0.7%.
Example 6
The methanol solution that in reactor, adds 70 gram alpha, beta-lonones and 30 gram γ-jononeionones and 100 milliliters, the cuprous chloride that adds 3 grams then, at 30 ℃ down is the UV-irradiation 0.5 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 95.5 grams.
By gas chromatographic analysis, record that alpha, beta-lonone content is 97% in the product, α-Zi Luolantong content is 0.9%.
Example 7
The methanol solution that in reactor, adds 20 gram α-Zi Luolantongs, 30 gram γ-jononeionones, 50 gram alpha, beta-lonones and 100 milliliters, the cuprous chloride that adds 3 grams then, at 30 ℃ down is the UV-irradiation 0.5 hour of 325 nanometers with wavelength, add 200 milliliters of usefulness of water (50MLx3) ethyl acetate extraction at last, solvent evaporated, underpressure distillation get product 96.5 grams.
By gas chromatographic analysis, record that alpha, beta-lonone content is 97.5% in the product, α-Zi Luolantong content is 0.4%, γ-jononeionone content is 0.4%.
Claims (3)
1. the method for preparing the high purity alpha, beta-lonone, this method is made up of following steps:
(1) cuprous chloride with jononeionone and jononeionone quality 2～3% is dissolved in the methyl alcohol;
(2) at room temperature be the UV-irradiation 0.5～1 hour of 300～325nm with wavelength;
(3) add the water ethyl acetate extraction, solvent evaporated, underpressure distillation gets the product of purity 〉=98.5% of alpha, beta-lonone;
Described jononeionone is one or both in α-Zi Luolantong, the γ-jononeionone, or the mixture of one or both and alpha, beta-lonone in the α-Zi Luolantong, γ-jononeionone; The volume of used methyl alcohol is 1～1.5 times of jononeionone quality.
2. the method for claim 1 is characterized in that described ultraviolet wavelength is 325nm.
3. method as claimed in claim 1 or 2 is characterized in that described step (1) for jononeionone is dissolved in methyl alcohol, adds the cuprous chloride of jononeionone quality 2～3% then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101991970A CN101381293B (en) | 2008-10-16 | 2008-10-16 | Method for preparing high-purity beta-jonone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101991970A CN101381293B (en) | 2008-10-16 | 2008-10-16 | Method for preparing high-purity beta-jonone |
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| Publication Number | Publication Date |
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| CN101381293A CN101381293A (en) | 2009-03-11 |
| CN101381293B true CN101381293B (en) | 2011-11-16 |
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| CN2008101991970A Active CN101381293B (en) | 2008-10-16 | 2008-10-16 | Method for preparing high-purity beta-jonone |
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| CN108031476B (en) * | 2017-11-24 | 2020-07-24 | 万华化学集团股份有限公司 | Catalyst for preparing β -ionone, preparation method thereof and method for preparing β -ionone by using catalyst |
| CN109665977B (en) * | 2018-12-21 | 2021-06-15 | 广州百花香料股份有限公司 | Efficient production method of ionone-alpha sodium hydroxysulfonate adduct |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508113A (en) * | 2002-12-19 | 2004-06-30 | 上海应用技术学院 | Industrial method for preparing beta-ionone |
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2008
- 2008-10-16 CN CN2008101991970A patent/CN101381293B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508113A (en) * | 2002-12-19 | 2004-06-30 | 上海应用技术学院 | Industrial method for preparing beta-ionone |
Non-Patent Citations (2)
| Title |
|---|
| 吴洪伟等.羰基铁催化法提纯β- 紫罗兰酮反应的研究.《烟草科技/ 烟草化学》.2000,(第4 期),第24-25页. * |
| 陈立军等.高纯度β2紫罗兰酮的制备方法.《香料香精化妆品》.2005,(第3 期),第29-32页. * |
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Denomination of invention: Method for preparing high-purity beta-jonone Effective date of registration: 20200107 Granted publication date: 20111116 Pledgee: Bank of China, Limited by Share Ltd, Guangzhou, Panyu branch Pledgor: Guangzhou Wisdom Bio-Technology Co., Ltd. Registration number: Y2020440000002 |
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Address after: 510555 No.78 Fenghuang SANHENG Road, Zhongxin Guangzhou Knowledge City, Huangpu District, Guangzhou, Guangdong Province Patentee after: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. Address before: 510530, 17, Fenghuang three road, Guangzhou, Guangzhou, Guangdong, China, five rooms 450 Patentee before: GUANGZHOU WISDOM BIO-TECHNOLOGY Co.,Ltd. |
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